Water-soluble phthalocyanine dyestuffs and process for preparing them



United States Patent Office 3,409,633 Patented Nov. 5, 1968 3 409 633 WATER-SOLUBLE RHTHALOCYANINE DYE- g' r lg s AND PROCESS FOR PREPARING Hartmut Springer, Frankfurt am Main, Germany, assignor to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany,

a corporation of Germany No Drawing. Filed Mar. 23, 1965, Ser. No. 442,197

Claims priority, application Germany, Mar. 26, 1964,

F 8 Claims. c1.260 314.s

The present invention relates to new water-soluble phthalocyanine dyestuffs and to a process for preparing them; in particular, the invention relates to phthalocyanine dyestuffs of the general formula R1 SOz-CHa-CH:OS 03H] in which Pc represents a metal-containing phthalocyanine nucleus which may be substituted by groups which do not part solubility in water, Z represents the group of the formula -(CH or the group of the formula cH2),NR2 in which q stands for an integer from at least 2 and at most 4.

Belgian Patent No. 600,946 describes water-soluble phthalocyanine dyestuffs of the formula in which Pc represents a metal-containing phthalocyanine nucleus and X represents a bivalent organic radical, for example, the group (CH or the group the benzene nucleus A may contain further substituents, for example, a nitro group, and m and n stand for integers from 1 to 3, the sum of m and n not exceeding 4.

The known dyestufifs of Formula 1 may be prepared, for example, by condensing amines of the Formula 2 in which X is defined as above and benzene nucleus A may be substituted in the manner described above, with vide complete condensation and sulfonamide formation of all the sulfonic acid chlon'de groups present in the phthalocyanine derivative used.

Now I have found cyanine dyestuffs of the that new water-soluble phthalogeneral Formula 3.

water, Z represents the group (CH or the group (CH NR in which q stands for an integer from 1 to 6 the sum of a and b at least 2 and at most 4, can be prepared by condensing amines of the general Formula 4 H SOzCHz-CH2OH R1 wherein R and Z are defined as above and the benzene nucleus A may be substituted in the manner described metal sulfite.

When carrying out the It is characteristic of the water-soluble reactive dyewhich correspond to hydroxy, alkoxy, carboxylic acid, or nitro groups as well as halogen atoms.

i iestas rials for the process of the present invention are, for example, di-, trior tetrasulfonic acid chlorides of metalcontaining phthalocyanines or mixturesthereof, wherein the sulfonic acid chloride groups are present either at the benzene nuclei of the macrocyclic ring or at annulated rings or at aryl radicals which may be linked directly or by means of bridge members, such as CO- or -SO to the phthalocyanine nucleus. As complex-bound metals in the phthalocyanine nucleus P of the metal-containing phthalocyanine derivatives of the type mentioned above there may be mentioned, for example, copper, nickel, cobalt or iron. Suitable sulfonic acid chlorides are for example the following: copper phthalocyanine-(3) tetrasulfonic acid chloride, copper phthalocyanine-(4)-tetrasulfonic acid chloride, copper phthalocyanine-(3)-tri-sulfonic acid chloride, nickel phthalocyanine-(3)-tetrasulfonic acid chloride, copper phthalocyanine-(3)-disulfonic acid chloride and tetraphenyl-copper-phthalocyanine-tetrasulfonic acid chloride.

e The metal-containing phthalocyanine-sulfonic acid chlorides used as startingsubstances according to the process of the invention can be prepared in known manner, for example by treating the corresponding metal-containing phthalocyanines or phthalocyanine-sulfonic acids with chlorosulfonic acid. The sulfochlorination can be effected, if desired, in the presence of carbon tetrachloride or chlorides of acids, such for example as thionylchloride or phosphorus pentachloride, in the manner described for example in German Patent No. 891,121.

As araliphatic amines of Formula 4 containing p-hydroxyethylsulfonyl groups there may be used for the condensation with the corresponding metal-containing phthalocyanine-sulfonic acid chlorides according to the process of the invention derivatives having an unsubstituted amino group as well as N-alkylamines. Among the amines of Formula 4 there may be mentioned, for example the following:

fl-Hydroxyethyl-[4-(B-aminoethyD-phenyl]-sulfone of the formula rrm-cm-crn-Q-sm-cm-cHz-orr (5) N-[2-nitro-4-(B hydroxyethylsulfonyl)-phenyl]-ethylenediamine of the formula Gri l 1-[2'-nitro-4-(B hydroxyethylsulfonyl) phenyl1-piperazine of the formula CHr-CH;

N CIITCHZ OzN (7) N-(p-hydroxyethyl) N-[Z-methoxy-S-(B-hydroxyethylsulfonyl)-phenyl]-ethylene-diamine of the formula The amines corresponding to Formulae 5 to 8 given above can be obtained according to the usual processes for the manufacture of such compounds, The compound of Formula 5, for example, is obtained in the form of its hydrochloride by converting Nacetyl-[B-phenylethylaminc by treatment with chlorosulfonic acid into the 4-[(B- acetylamino)-ethyl] -benzenesulfonic acid chloride, the latter is reduced to form the corresponding sulfonic acid which is reacted with ethylene oxide or fi-chloroethanol; the reaction product is then hydrolized with hydrochloric acid. The amine of Formula 7 can be prepared, for exhthalocyanine derivatives suitable as starting matefrom about 5 ample, byreacting fi-hydroxyethyl-[(3-nitro-4-chloro)- phenyl1-sulfone with piperazine.

For carrying out the process of the present invention the amines of the general Formula 4 can be used either in the form of free bases or in the form of their watersoluble hydrohalic acid addition saltsJ,

The reaction of phthalocyanine-sulfonic acid chlorides with the amines of the general Formula 4 whichconstitutes the. first stage.of.the process of the present invention canbe carried out in an aqueous or non-aqueous medium, depending on the solubility-of the reactants used in solution or in suspension, in the presence of acidbinding agents. For the reaction in a non-aqueous medium there may be used organic solvents or diluents, such for example as methanol, dimethylformamide or pyridine. Suitable acid binding agents are, for example, sodium bicarbonate, sodium carbonate, sodium hydroxide, tertiary organic bases, such as pyridine or triethylamine, or an excess of the amines of the general Formula 4. The reaction is carried out at pH-values in a weakly acid to alkaline range. The temperature required for the reaction may vary within wide limits. It is usually within the range It is characteristic of the first stage of the process of the present invention that the amount of amines of the general Formula 4 used should be calculated so as to ensure that all the sulfonic acid chloride groups of the phthalocyanine-sulfonic acid chlorides are reacted to form sulfonamide groups so that hydrolysis of the sulfonic acid chloride groups into sulfonic acid groups is avoided or can only take place on a very small scale. If, nevertheless, a slight hydrolysis takes place in the course of the reaction, the saponification products formed can be separated from the reaction product without difficulty due to their higher solubility in water.

The second stage of the process of the invention, i.e. the conversion of the phthalocyanine-sulfonamides, which contain B-hydroxyethylsulfonyl groups and are obtained on the first stage of the process, into their sulfuric acid esters is carried out in known manner either by treating the sulfonamides with sulfuric acid or by reacting them with chlorosulfonic acid or sulfur trioxide or their complex compounds with tertiary amines, preferably in a tertiary amine as solvent.

On the second stage of the process of the invention dyestuffs of the general Formula 3 are obtained wherein-in accordance with the number of sulfonic acid chloride groups present in the phthalocyanine compound used as starting substance-a has the value of 2-4 and b has the value of 0. If it is desirable to obtain dyestuffs of Formula 3 wherein the value b does not equal 0, the second stage of the process must be followed by a third reaction stage. On the third stage, the dyestuffs containing fi-hydroxy-ethylsulfonyl-sulfuric acid ester groups which have been obtained after the first two stages are treated with an alkali metal sulfite, for instance with so,- dium sulfite. This treatment has the effect of transforming a part of the ,G-hydroxyethylsulfonylsulfuric acid ester groups contained in the dyestufi molecule according to the following reaction equation F-[SOzCHz-CH2OSOsHhi-p-l-UNMSOg )SOZ CHZ'CHZ"OSOBH]I\ F\ b.Na2S04 ISOr-CHg-CHz-SOsHlb in which F stands for the dyestuif radical, into B-sulfoethylsulfonyl groups. The amount of alkali metal sulfite required for stage 3 should always be calculated so as to ensure that at least one sulfuric acid ester group of the dyestufi' molecule remains unmodified.

The new phthalocyanine dyestuffs obtainable according to the process of the invention can be used for dyeing and printing various materials, for example wool, silk, leather or linear polyamides. In particular, the new dye stuffs are suitable for dyeing and printing cellulose-containing materials of fibrous structure, such as linen, regenerated cellulose and, aboveall, COlZtOIlyThfi 'dyestufls are applied to the cellulose fibre for example by treating the material with an aqueous solution of-the dyestutf and with an aqueous solution of an agent having an alkaline reaction or an acid-binding agent, such as sodium hydroxide, sodium bicarbonate, trisodiurn, phosphate or sodium sulfide, or bytreatment with a printing paste containing the dyestufif and an acid-binding agent.-In-addition to acid-binding agents or substances capable .ofyielding. acid-binding agents the dyestutf solutions 'or pr-inting pastes maycontain urea, urethanes or water-soluble amides of aliphatic carboxylic acids, :such, for-example, as formamide, acetamide or malonic acid diamide. The treatment with acid-binding agents may be carried out before, during or after the application of the dyestulf, if desired, at an elevated temperature. t

On the materials mentioned yield dyeing and prints having clear shades ranging from blue to green, which are distinguished by good fastness properties to light and to chlorine ,and generally by very obtained in Examples 4 and 5,

cording to the process of the invention are distinguished by considerably better properties of wet fastness.

The following examples serve to illustrate the invenare dissolved in 600 parts of water. 24 parts of a 33% sodium hydroxide solution are added to this solution arid then 48.5 parts of copper phthalocyanine-(3)-tetrasul* fonic acid chloride are introduced 'in the form of a moist above the:- new dyestuffs filter cake. The mixture is then heated to C. While being thoroughly stirred, and the pH-value iskept-at' 9:5 to 10 by portionwise addition of about 100 parts of -2 N-sodium hydroxide solution. As soon as-n'o more sodium hydroxide solution is consumed the product formed is filtered, washed with warm water until a colorless filtrate runs off and dried at 100 C. The dry reaction product obtained in this manner is introduced in the form of a finely ground powder into 700 6 Example 2 116 arts of 'N [2 nitro-4 (e hydroxyethylsulfonyl)- phenyl]-e thylene-diamine (melting point: l51l52 C.) of the formula v I p y y which can. beppepared .by reacting fl-hydroxyethyl-(S- nitroA-Chloro)-phenyl:sulfone with ethylene-diamine, are suspended ,in 3000 parts of water. The suspension is heated to 50 C., and, while thoroughly stirring, 97 parts of copper phthalocyanine-(3)-tetrasulfonic acid chloride are introduced in the form of a moist paste, the pH-value being maintained at 9-9.5 by dropwise addition of about 270 parts of 2 N-sodium hydroxide solution. As soon as the condensation is terminated the product obtained is filtered and washed thoroughly with warm water. The moist filter cake is then stirred up with dilute hydrochloric acid, the product is filtered again, washed with water until neutral and dried at C. The dry condensation product is introduced in. the form .of a finely ground powder into 1650 parts of concentrated sulfuric acid and the whole is stirred for'several hours at room temperature. The solution obtained is poured onto a mixture of ice and NaCl solution, the precipitated dyestuif is filtered and washed with NaCl solution until neutral.

The moist filtration residue is then dissolved in 3000 parts of water; if the solution shows still a weakly acid reaction it is neutralized by addition of sodium bicarbonate. Subsequently, a solution of 50.4 sodium sulfite in 200 OrN CuPc

The dyestutf is for dyeing and print ng a cotton fabric in the presence of Example 3 Parts of the hydrochloride of B-hydroxyethyl-[4-(flaminoethyll-phenyl]-sulfone corresponding to the forparts of a salt-containing turquoise-blue dyestutl which shows similar scribed in Example 1 and which corresponds to the following formula Example 4 11.5 parts of the hydrochloride of fl-hydroxyethyl-[ i- (,H-ammoethyl)-phenyl]-sulfone corresponding to the formula given invthe first paragraphof Example 11 are hydroxide solution is consumed, the condensationproduct condensed in theimanner described in Examples ,1, to-3 formed is filtered and washed thoroughly with water. The with 12.7 parts of 'tetraphenyl-copper-phthalocyaninefiltration residue is dried, finely pulverized and then intetrasulfonic acid chloride which is used in the form of troduced into 140 parts of concentrated sulfuric acid and a moist paste. 20 parts of the condensation product are stirred for 14 hours at room temperature. Subsequently, obtainedwhich is converted into its sulfuric acid ester in the solution obtained is poured into a mixture of sodium the manner described above. There are obtained 3lparts chloride solution and ice, the precipitated ester dyestuff of a salt-containing greendyestuffwhich is easily soluble is filtered and washed with a sodium chloride solution.

in water and resistant to 'washing when fixed on cotton Themoist filtration'residue is dissolved in 500 parts of fabrics with the aid of agents having an alkaline reaction. water and the solution is neutralized by addition of sodium The dyestutf obtained corresponds itothe following ,forbicarbonateg'The dyestuff is then isolated by salting out 'rnula. l, f witlf'sodium chloride." After drying, parts of a salt- Example l containing turquoise-blue dyestufi' are obtained which corresponds to the following formula 97 parts of copper phthalocyanine-(3)-tetrasulfonic acid chloride are condensed in the manner described in Example 2 with 130 parts of N-[2-nitro-4'-(B-hydroxyethylsulfonyl)-phenyl]-piperazine of the following formula The dyestuff is very easily soluble in water and resistant excellently to washing when fixed on cotton fabrics with a the aid of agents having an alkaline reaction.

(melting point: 162-164 C.) which can be prepared by The N (fi hydmxyathyl) N, [z methoxy 545L113, reaction of p-h droxyethyl-(3-n1tro-l-c l )-P Y droxyethyl-sulfonyl)-phenyl]-ethylene-diamine of the forfone w th prperazme. The condensation product is conmula given above used as starting product for the preparaverted into its sulfunc acidr ester by means of sulfuric tion of the dyesmfi mentioned above can be Prepared in acid. A green dyestuff is obtained which corresponds to the following manner:

the following formula By diazotizing p-hydroxyethyl (3-amino-4-methoxyphenyl)-sulfone and coupling the diazomum salt obtained with diethanolamine-disulfuric acid ester in an alkaline CHa-CH:

. sodium carbonate solution, the monosulfuric acid ester of CuPo-[SOg-N N -SOZ-'CHTCH1-OSO3mJ 5 1-[2'-methoxy-5 (fi-hydroxyethylsulfonyl)-phenyl] 3- CHFog (pf-hydroxyathyl)-4,5-dihydro-l,2,3-triazole is obtained N0, in the form of an inner salt (melting point: 201 C.)

correpsonding to the following formula It is easily soluble in water and dyes wool and cotton green shades having excellent fastness properties. 00H;

Example 6 @351? IIICHaCH2OSOa 19 parts of N-(fiy v y Y- 5" HHHZ hydroxyethylsulfonyl)-phenyl]-ethylene-diamine of the Q (.3112 GET-s0 formula During the hydrolysis of this compound with hydrochloric C1110 acid the sulfuric acid ester group is split off and 1-[2- methoxy-S' g (fi-hydroxyethylsulfonyl)-phenyl] 3-03- HOCHiCHznrhydroxyethyl) 4,5?dihydro-1,2,3-triazolium chloride is r formed melting at 144 C. Catalytic hydrogenation of SOT'CHPCHT'OH this product with hydrogen and Raney nickel yields N- (B-hydroxyethyD-N [Z-methoxy-S-(B hydroxyethylsulfonyl)-phenyl]-ethylenediarnine of the formula given which is prepared as described below, are dissolved 1n in the fi t paragraph fthi example, in the f f a 200 parts of water. 9.7 parts of copper phthalocyamnecolorless oil, while splitting g ammonia (3)-tetrasulfonic acid chloride are introduced into this v solution in the form of a moist paste, the pH-value of P the solution is adjusted to 8.5 by addition 0f 2 N-sodium parts of a, copper phthalocyanine-(3)-sulfonic acid hydroxide solution, the reaction mixture is heated to 50 chloride containing about 2.2 ,sulfonic acid chloride C. and stirred for some hours at this temperature. During groups are introduced into a solution of 85 parts of the the reaction time the pH-value is maintained by continuhydrochloride of ,B-hydroxyethyl [4-( 8 aminoethyl)- ous addition of 2 N-sodium hydroxide solution. As soon phenyl1-sulfone in 850 parts of water, the pH-value of as the condensation is terminated and no more sodium which has been adjusted to 9.5 by means of sodium hydroxide solution. The reaction mixture is heated to 50 and stirred for several hours at this temperature, the pH-value being maintained at 9.5 by continuous addition of a 2 N-sodium hydroxide solution. As soon as no more sodium hydroxide solution is consumed, the product formed is filtered and stirred for several hours at room temperature. Working-up is carried out in the manner described in Example 1, and 169 parts of a salt-containing blue dyestulf are obtained which is easily soluble in water and dyes wool and cotton turquoise-blue shades having excellent fastness properties. The dyestutf corresponds to the following formula I claim: 1. The Water-soluble phthalocyanine dyestulf of the formula 2. The water-soluble phthalocyanine dyestufi' of the formula 3. The water-soluble phthalocyanine dyestutf of the formula C uPc [SOz-NH CHg-CHz-NH-Q-SorCHrCHrSOzHh l zN 4. The Water-soluble phthalocyanine dyestufl of the formula 5. The Water-soluble phthalocyanine dyestuff of the formula [Tetraphenyl-O uPc 6. The water-soluble phthalocyanine dyestutf of the formula 7. A Water-soluble phthalocyanine dyestuff of the formula can be piperazine.

8. A water soluble phthalocyanine dyestufl of the formula in which Pc represents copper phthalocyanine, nickel phthalocyanine or copper tetraphenyl phthalocyanine R R represents of 0 to 3, the sum of a and b being at least 2 and at most 4, and the group R R I A z)q N can be piperazine.

References Cited UNITED STATES PATENTS 3,062,830 11/1962 Buc et al. 260314.5 3,133,059 5/1964 Clark et al 260-314.5 3,148,933 9/1964 Randall et al 260-3145 3,235,540 2/1964 Dortmann et al. 260314.5 3,238,221 3/1966 Schmitz et al. 260314.5

FOREIGN PATENTS 1,286,992 1/1962 France.

HENRY R. JILES, Primary Examiner. H. I. MOATZ, Assistant Examiner. 

1. THE WATER-SOLUBLE PHTHALOCYANINE DYESTUFF OF THE FORMULA 